CN1181155C - Hydrofluorocarbon compositions - Google Patents

Hydrofluorocarbon compositions Download PDF

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CN1181155C
CN1181155C CNB971995761A CN97199576A CN1181155C CN 1181155 C CN1181155 C CN 1181155C CN B971995761 A CNB971995761 A CN B971995761A CN 97199576 A CN97199576 A CN 97199576A CN 1181155 C CN1181155 C CN 1181155C
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composition
fluorochemical
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CN1237197A (en
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Vm
V·M·菲利克斯
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B·H·米诺尔
ά
A·C·斯维尔特
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EIDP Inc
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EI Du Pont de Nemours and Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C19/00—Acyclic saturated compounds containing halogen atoms
    • C07C19/08—Acyclic saturated compounds containing halogen atoms containing fluorine
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
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    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/149—Mixtures of blowing agents covered by more than one of the groups C08J9/141 - C08J9/143
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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/30—Materials not provided for elsewhere for aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C08J2207/04—Aerosol, e.g. polyurethane foam spray
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/12—Hydrocarbons
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/22—All components of a mixture being fluoro compounds
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/32—The mixture being azeotropic

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Abstract

The present invention relates to the discovery of compositions which include fluoroethane, 2-fluoropropane or tert-butylfluoride. These compositions are useful as pure components or with at least one of tetrafluoroethane, difluoroethane, hexafluoropropane, a hydrocarbon or dimethylether. These compositions are useful as aerosol propellants, refrigerants, cleaning agents, expansion agents for polyolefins and polyurethanes, refrigerants, heat transfer media, gaseous dielectrics, fire extinguishing agents, power cycle working fluids, polymerization media, particulate removal fluids, carrier fluids, buffing abrasive agents, and displacement drying agents.

Description

Hydrofluorocarbon compositions
Related application
The application requires the right of No. the 60/029th, 971, the U.S. Provisional Application submitted on November 4th, 1996.
Invention field
The present invention relates to following discovery, promptly comprise fluoroethane, the composition of 2-fluoropropane or tertiary butyl fluorine.These compositions are as pure component, perhaps with Tetrafluoroethane, and C2H4F2 C2H4F2, HFC-236fa, at least a combined utilization has purposes in hydrocarbon or the dimethyl ether.
These compositions can be used as aerosol propellants, cooling agent, sanitising agent, the swelling agent of polyolefine and polyurethanes, cooling agent, heat-transfer medium, gaseous dielectric medium, fire-fighting medium, power circulating working fluid, polymerisation medium, clearance of particles fluid (particulate removal fluid), carrying object, the polishing abrasive, and the displacement siccative uses.
Background of invention
Fluorinated hydrocarbons has many purposes, and for example as aerosol propellants, whipping agent and cooling agent, these compounds comprise trichlorofluoromethane (CFC-11), Refrigerant 12 (CFC-12) and chlorodifluoromethane (HCFC-22).
The someone points out in recent years, and the fluorinated hydrocarbons of some kind is discharged into the atmosphere, and stratospheric ozonosphere is had adverse influence.Though this proposal is not accepted fully,, formed the motion that some Chlorofluorocarbons (CFC) and hydrochlorofluorocarazeotropic (HCFC) compound were used and produced in a kind of control according to an international agreement.
People also have demand for aerosol propellants and the whipping agent that photochemical activity is markedly inferior to hydro carbons, and hydro carbons is one of reason that causes smog on environment ozone and the ground.These compounds typically are known as low VOC (volatile organic compound, volatile organic compounds) or non-VOC.
Therefore, require to have than existing cooling agent and have lower ozone depletion potential (ozonedepletion potential) and performance still can meet the demands on the refrigeration purposes improved cooling agent.Because HFC is not chloride and therefore ozone depletion potential (ozone depletion potential) be zero, so hydrogen fluorine carbon (HFC) is proposed and is used for substitute CFC and HCFC.
On the refrigeration purposes, by axle envelope, often scatter and disappear when welded contact and damaged these leaks of pipeline by hose connection place in operation for cooling agent.In addition, cooling agent may be discharged into the atmosphere in the chilling unit maintenance process.If cooling agent is not pure component, azeotrope or Azeotrope-like, when its seepage or when being dispersed in the atmosphere, this cooling agent is formed and may be changed from chilling unit.The variation that cooling agent is formed can make cooling agent become inflammable substance or reduce its refrigeration performance.
Therefore, wish only to use fluorinated hydrocarbons contain the azeotropic of one or more fluorinated hydrocarbons or Azeotrope-like as cooling agent.
Be divided into the fluorinated hydrocarbons of low VOC or non-VOC class,, therefore also be used as aerosol propellants or whipping agent because they can not cause on the significant ground and pollute.
Fluorinated hydrocarbons also can be used as sanitising agent or cleaning solvent, for example solvent of cleaning circuit plate.Because in vapor degreasing operation sanitising agent usually will be in final rinsing be cleaned by redistillation with re-use, be azeotrope or Azeotrope-like so wish this clean-out system.
Comprise the whipping agent that the azeotrope of fluorinated hydrocarbons or Azeotrope-like also can be used as the thermoplastic foam of making closed-cell polyurethane and phenoplast, as heat-transfer medium, gaseous dielectric, fire-fighting medium or for example be used for the power circulating working fluid etc. of vapour pump.These compositions also can as remove the particulate fluid from the metallic surface, can be used as carrying object and use as the inert media of polyreaction, for example, the auxilliary film of putting lubricant on metal parts perhaps as the polishing abrasive, is removed the polishing polishing compounds from glazed surface such as metal covering.They can also for example dewater from jewel or metal parts as the displacement siccative of dehydration, as Resist development agent commonly used in the circuit manufacturing technology, comprise chlorine type photographic developer, perhaps when using with for example chlorocarbon such as 1 or trieline as light carving rubber stripper.
Summary of the invention
The present invention relates to following discovery, promptly comprise the composition of fluoroethane, 2-fluoropropane or tertiary butyl fluorochemical.These composition ozone depletion potential (ozone depletion potential, ODP) be zero, make the potential of Global warming low, be the VOC lower than hydro carbons volatility, these compositions are as pure component, perhaps with Tetrafluoroethane, and C2H4F2 C2H4F2, HFC-236fa, at least a application together has purposes in hydrocarbon or the dme.These compositions can be used as swelling agent, heat-transfer medium, gaseous dielectric medium, fire-fighting medium, power circulating working fluid, polymerisation medium, clearance of particles fluid, carrying object, the polishing abrasive of aerosol propellants, cooling agent, sanitising agent, polyolefine and polyurethanes, and the displacement siccative uses.
Moreover, the present invention relates to following discovery, i.e. two-pack azeotrope or Azeotrope-like.Said composition comprises: the fluoroethane of significant quantity, 2-fluoropropane or tertiary butyl fluorochemical; And as Tetrafluoroethane, C2H4F2 C2H4F2, HFC-236fa, hydrocarbon or the dme of second component, to form azeotrope or Azeotrope-like.Wish very that concerning cooling agent it is an azeotrope, but then optional to aerosol propellants.
Compound of the present invention comprises following component:
1. ethane (HFC-161, or CH 3CH 2F, boiling point=-38 ℃),
2.1,1,2,2-Tetrafluoroethane (HFC-134, or CHF 2CHF 2, boiling point=-20 ℃),
3.1,1,2,2-Tetrafluoroethane (HFC-134a, or CF 3CH 2F, boiling point=-26 ℃),
4.1,1-C2H4F2 C2H4F2 (HFC-152a, or CH 3CHF 2, boiling point=-25 ℃),
5.2-fluoro-propane (HFC-281ea, or CH 3CHFCH 3, boiling point=-11 ℃),
6. tertiary butyl fluorochemical (HFC-3-10-lsy, or (CH 3) 3CF, 12 ℃ of boiling points),
7.1,1,1,2,3,3-HFC-236fa (HFC-236ea, or CF 3CHFCHF 2, boiling point=6 ℃),
8.1,1,1,3,3,3-HFC-236fa (HFC-236fa, or CF 3CH 2F 3, boiling point=-1 ℃),
9. dimethyl ether (DME, or CH 3OCH 3, boiling point=-25 ℃),
10. butane (CH 3CH 2CH 2CH 3, boiling point=-0.5 ℃),
11. Trimethylmethane ((CH 3) 3CH, boiling point=-12 ℃),
12. propane (CH 3CH 2CH 3, boiling point=-42 ℃),
According to Grosse and Lin at J.Org.Chem., Vol.3, report among the pp 26-32 (1938), HFC-161 (CAS registration number 353-36-6) and HFC-281ea (sec.-propyl is fluoridized thing, CASs registration number 420-26-8) can by hydrogen fluoride respectively with ethene and propylene prepared in reaction.
2-fluoro-2-methylpropane (tertiary butyl fluorochemical, HFC-3-10-ly, CAS registration number [353-61-7]) can be according to Milos Hudlicky work " organic fluoride chemistry " second edition, record is formed by the trimethyl carbinol and aqueous hydrogen fluoride solution prepared in reaction in 1976,689 pages.
The accompanying drawing summary
The gas/liquid profile of equilibrium figure of mixture HFC-161/HFC-134a when Fig. 1 is-14.15 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/HFC-152a when Fig. 2 is-0.05 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/HFC-281ea when Fig. 3 is-10 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/HFC-3-10-lsy when Fig. 4 is-20 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/ butane when Fig. 5 is-20 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/ Trimethylmethane when Fig. 6 is-10 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-161/DME when Fig. 7 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-281ea/HFC-134a when Fig. 8 is-10 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-281ea/HFC-152a when Fig. 9 is-10.01 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-281ea/HFC-3-10-lsy when Figure 10 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-281ea/ propane when Figure 11 is-10 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-281ea/DME when Figure 12 is-9.95 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/HFC-134 when Figure 13 is-21.7 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/HFC-134a when Figure 14 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/HFC-152a when Figure 15 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/HFC-236ea when Figure 16 is-1.7 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/HFC-23fa when Figure 17 is-2.5 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/ butane when Figure 18 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/ Trimethylmethane when Figure 19 is 0 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/ propane when Figure 20 is-20 ℃;
The gas/liquid profile of equilibrium figure of mixture HFC-3-10-lsy/DME when Figure 21 is-10 ℃.
                     Detailed Description Of The Invention
The present invention relates to following composition:
(a) fluoroethane (HFC-161);
(b) 2-fluoro-propane (HFC-281ea);
(c) tert-butyl group fluoride (HFC-3-10-lsy);
(d) HFC-161 and HFA 134a (HFC-134a); HFC-161 and 1,1-Difluoroethane (HFC-152a); HFC-161 and 2-fluoro-propane (HFC-281ea); HFC-161 and tert-butyl group fluoride (HFC-3-10-lsy); HFC-161 and butane; HFC-161 and iso-butane; Or HFC-161 and dimethyl ether (DME);
(e) HFC-281ea and HFC-134a; HFC-281ea and HFC-152a; HFC-281ea and HFC-3-10-lsy; HFC-281ea and propane; Or HFC-281ea and DME; Or
(f) HFC-3-10-lsy and 1,1,2,2-HFC-134a (HFC-134); HFC-3-10-1sy and HFC-134a; HFC-3-10-lsy and HFC-152a; HFC-3-10-lsy and 1,1,1,2,3,3-HFC-236fa (HFC-236ea); HFC-3-10-lsy and 1,1,1,3,3,3-HFC-236fa (HFC-236fa); HFC-3-10-lsy and butane; HFC-3-10-lsy and iso-butane; HFC-3-10-lsy and propane; Or HFC-3-10-lsy and DME.
Each component of 1-99% in the composition (weight) can be used as swelling agent, refrigerant, heat transfer medium, gaseous dielectric, extinguishing chemical, power circulating working fluid, polymerisation medium, clearance of particles fluid, carrying object, the polishing grinding agent of aerosol propellants, refrigerant, cleaning agent, polyolefin and polyurethanes, and the displacement drier etc. Moreover, the invention still further relates to following new discovery, i.e. azeotropic mixture or Azeotrope-like, said composition comprises above-mentioned each mixture of effective dose to form azeotropic mixture or Azeotrope-like.
" azeotropic mixture " composition means the mixture that constant boiling point is arranged of two or more materials, and its behavior is identical with one matter. A kind of method that characterizes azeotropic mixture is, the steam that is produced by part evaporation or liquid distillation has identical forming with the liquid that is evaporated or distill, and that is to say that the mixture of distillate phegma does not have the change of composition. Compared by the non-azeotropic mixture that same composition consists of with those, azeotrope can be considered to have the composition of azeotropic characteristics because they demonstrate or high or minimum boiling point.
" Azeotrope-like " means the mixture of the boiling point of the constant boiling point of having of two or more materials or substantial constant, and its behavior is identical with one matter. A kind of method that characterizes Azeotrope-like is, by liquid partly evaporate or distill and the steam that produces and the liquid that is evaporated or is distilled by substantially the same forming, that is to say that the mixture of distillate/phegma is gone up the change that does not have composition substantially. The another kind of method that characterizes Azeotrope-like is that bubble point steam pressure and the dew point steam pressure of composition under specified temp is basic identical.
Those skilled in the art are known, if a kind of composition is Azeotrope-like, with for example the evaporation or the boiling method remove the said composition of 50% (weight) after, when measuring with absolute unit, the vapour pressure of former composition and removed the former composition of 50% (weight) after gap between the vapour pressure of remaining composition less than about 10%. Absolute unit means the pressure according to the calculating of following unit, for example, and the term of the equivalence that Pascal, atmospheric pressure, bar, holder, dynes/cm, millimetres of mercury, inches of water(in H2O) and other those skilled in the art are in common knowledge. If azeotropic mixture, then there is not difference between the vapour pressure of remaining composition in the vapour pressure of former composition and after having removed the former composition of 50% (weight).
Therefore, the composition that is included in the scope of the present invention is the composition that contains the following composition of effective dose:
(a) HFC-161 and HFA 134a (HFC-134a); HFC-161 and 1,1-Difluoroethane (HFC-152a); HFC-161 and 2-fluoro-propane (HFC-281ea); HFC-161 and tert-butyl group fluoride (HFC-3-10-lsy); HFC-161 and butane; HFC-161 and iso-butane; Or HFC-161 and dimethyl ether (DME);
(b) HFC-281ea and HFC-134a; HFC-281ea and HFC-152a; HFC-281ea and HFC-3-10-lsy; HFC-281ea and propane; Or HFC-281ea and DME; Or
(c) HFC-3-10-lsy and 1,1,2,2-HFC-134a (HFC-134); HFC-3-10-lsy and HFC-134a; HFC-3-10-lsy and HFC-152a; HFC-3-10-lsy and 1,1,1,2,3,3-HFC-236fa (HFC-236ea); HFC-3-10-lsy and 1,1,1,3,3,3-HFC-236fa (HFC-236fa); HFC-3-10-lsy and butane; HFC-3-10-lsy and iso-butane; HFC-3-10-lsy and propane; Or HFC-3-10-lsy and DME;
So that form remaining composition at the former composition of 50% (weight) after evaporation or boiling are removed, the difference between former composition vapour pressure and the remaining set compound vapour pressure is 10% or less.
Concerning azeotropic mixture, certain compositing range is arranged near azeotropic point usually, to the azeotropic mixture of maximum boiling point is arranged, its boiling point under specified pressure is higher than the boiling point of each pure component of said composition under that pressure, and its vapour pressure under specified temp is lower than the vapour pressure of each pure component of said composition under that temperature, and to the azeotropic mixture of minimum boiling point is arranged, its boiling point under specified pressure is lower than the boiling point of each pure component of said composition under that pressure, and its vapour pressure under specified temp is higher than the vapour pressure of each pure component of said composition under that temperature. Be higher or lower than the boiling temperature of pure component and steam pressure and be by the expectation between the molecule of composition not the row active force cause that molecular separating force can be for example resultant effect of Van der Waals force and hydrogen bond of repulsive force and attraction.
Under specified pressure the highest or minimum boiling point is arranged, the variation of its vapor pressure can be identical or different less than 10% compositing range when compositing range that maximum or minimum steam press and those compositions that evaporates 50% (weight) were perhaps arranged under specified temp.Under specified pressure, have the highest or minimum boiling point or when under specified temp, having compositing range ratio under the situation that maximum or minimum steam press to evaporate the composition of 50% (weight) variation of vapor pressure wide less than about 10% compositing range, in this case, undesirable intermolecular forces is said for the refrigerant compositions fork-like farm tool used in ancient China with these power and is believed and remain important, with making it is not constant boiling point basically, but undesirable increase is showed in the variation of forming with cooling agent on usefulness or efficient.Boiling point substantially constant of the present invention, azeotropic or class azeotropic composition comprise following composition:
Component NTS T ℃ Weight range Preferable range
(wt.％/wt/％) (wt.％/wt.％)
HFC-161/HFC-134a -20 1-99/1-99 10-90/10-90
HFC-161/HFC-152a -30 1-99/1-99 10-90/10-90
HFC-161/HFC-281ea -10 73-99/1-27 73-99/1-27
HFC-161/HFC-3-10-lsy -20 75-99/1-25 75-99/1-25
HFC-161/ butane-20 67-99/1-33 67-99/1-33
HFC-161/ Trimethylmethane-20 52-99/1-48 52-9/1-48
HFC-161/DME -30 1-99/1-99 10-90/10-90
HFC-281ea/HFC-134a -10 1-99/1-99 10-90/10/90
HFC-281ea/HFC-152a -20 1-99/1-99 10-90/10-90
HFC-281ea/HFC-3-10-lsy 0 41-99/1-59 41-99/1-59
HFC-281ea/ propane-10 1-41/59-99 1-41/59-99
HFC-281ea/DME -9.95 1-99/1-99 10-90/10-90
HFC-3-10-lsy/HFC-134 -21.7 1-44/56-99 1-44/56-99
HFC-3-10-lsy/HFC-134a 0 1-32/68-99 1-32/68-99
HFC-3-10-lsy/HFC-152a 0 1-30/70-99 1-30/70-99
HFC-3-10-lsy/HFC-236ea-1.7 11-60/40-89 and 11-60/40-89 and
1-3/97-99 1-3/97-99
HFC-3-10-lsy/HFC-236fa -2.5 1-52/48-99 1-52/48-99
HFC-3-10-lsy/ butane 0 1-99/1-99 10-90/10-90
HFC-3-10-lsy/ Trimethylmethane 0 1-45/55-99 and 1-45/55-99 and
89-99/1-11 89-99/1-11
HFC-3-10-lsy/ propane-20 1-19/81-99 1-19/81-99
HFC-3-10-lsy/DME -10 1-42/58-99 1-42/58-99
For the purpose of the present invention, " significant quantity " is that the amount according to each component in the composition of the present invention defines, and when composition of the present invention mixes by this tittle, can form azeotrope or Azeotrope-like.This definition comprises the amount of each component, and this amount can change according to the pressure that is applied to said composition, as long as azeotrope or Azeotrope-like exist under different pressure, but has different boiling points.
Therefore, significant quantity comprises the amount of each component of composition of the present invention, for example represents with weight percentage, makes said composition form azeotrope or Azeotrope-like, its temperature and pressure not necessarily therewith the place point out identical.
For this argumentation, the azeotropic or the azeotropic meaning also are meant azeotropic or constant boiling point basically basically.In other words, the meaning that is comprised in these terms is the real azeotrope to introducing above still not, and comprises the component that containing of other is same but the composition of different ratios is arranged, and it is real azeotrope under other temperature and pressures; And comprise that those belong to the part of identical azeotrope system and are the composition of the equivalence of Azeotrope-like in nature.Known in the art is, the compositing range that one and azeotrope same composition are arranged, it will be not only show essentially identical character in refrigeration and other purposes, and will not emanate or have and can not fractionated tendency demonstrate its character substantially the same with real azeotrope will be according to boiling point constant characteristics or boiling the time.
In fact, can be by a kind of azeotrope that depends on selected condition and occur in a variety of forms of any discriminating in following several the standards.
* why certain composition can be called as A, B, C (and D ...) azeotrope, be that to this unique compositions, it requires A because azeotrope one speech also is conditional when being clear and definite, B, C (and D ...) such significant quantity is arranged, making it is azeotropic composition.
What * be well known to those skilled in the art is, under different pressure, the composition of given azeotrope will change to some extent at least to a certain extent, the variation of pressure also will change boiling temperature to a certain extent.Therefore, A, B, C (and D ...) azeotrope represent a unique types, depend on component relationship temperature and/or pressure, variable.Therefore, form through the composition of certain limit commonly used rather than with fixed and define azeotrope.
* said composition can be with A, B, C (and D ...) specified weight per-cent relation or molar percentage concern and define, will be appreciated that simultaneously such particular value only indicates a specific relation, and actually for a given azeotrope, by A, B, C (and D ...) represented a series of this relation exists really, and the influence that is stressed and changing.
* A, B, C (and D ...) azeotrope can be characterized, promptly defining said composition is an azeotrope that boiling point characterized that is used under the setting pressure.Given like this diagnostic characteristics does not limit the scope of the invention egregiously with several special composition data, and these several special compositions are limited by the tolerance range of used analytical equipment, and can only reach the tolerance range of used analytical equipment.
Azeotrope of the present invention or Azeotrope-like can make by any method commonly used, comprise the method for mixing or cooperating in the desired amount.Preferable methods is to mix in proper container after the component of weighing aequum.
Provide some concrete example explanation the present invention below, all per-cent all is weight percent, unless other explanation is arranged there.Be understandable that these examples just illustrate, and can not constitute limitation of the scope of the invention.
Example 1
Inter-state research
Inter-state research shows that following composition is an azeotropic, all is under assigned temperature.
Component T ℃ Weight range Vapour pressure
psia(kPa)
HFC-3-10-lsy/HFC-134 -21.7 13.9/86.1 14.7 101
HFC-3-10-lsy/HFC-236ea -1.7 33.6/66.4 14.7 101
HFC-3-10-lsy/HFC-236fa -2.5 12.7/87.3 14.7 101
Example 2
The influence of steam seepage
Under assigned temperature initial composition is installed in the container, the initial vapour pressure of said composition after measured.Keep under the constant situation from then on said composition being leaked out in the container in temperature,, at this moment measure the vapour pressure that remains in the composition in this container up to this original composition of removing 50% (weight).The result is summarized as follows.
After the weight % primary 50% of the weight %/B of A leaks
PSIA KPA PSIA KPA DELTA％P
HFC-161/HFC-134a(-20℃)
1/99 19.6 135 19.5 134 0.5
10/90 22.0 152 21.2 146 3.6
20/80 24.1 166 22.9 158 5.0
30/70 25.8 178 24.6 170 4.7
40/60 27.2 188 26.1 180 4.0
50/50 28.3 195 27.5 190 2.8
60/40 29.2 201 28.6 197 2.1
70/30 29.9 206 29.5 203 1.3
80/20 30.5 210 30.3 209 0.7
90/10 30.9 213 30.8 212 0.3
99/1 31.2 215 31.2 215 0.0
HFC-161/HFC-152a(-30℃)
1/99 11.7 80.7 11.7 80.7 0.0
10/90 12.7 87.6 12.3 84.8 3.1
20/80 13.8 95.1 13.1 90.3 5.1
30/70 14.9 103 14.0 96.5 6.0
40/60 15.9 110 14.9 103 6.3
50/50 16.9 117 15.9 110 5.9
60/40 17.8 123 16.9 117 5.1
70/30 18.7 129 18.0 124 3.7
80/20 19.5 134 19.0 131 2.6
90/10 20.3 140 20.0 138 1.5
99/1 20.9 144 20.9 144 0.0
HFC-161/HFC-281ea(-10℃)
99/1 44.9 310 44.8 309 0.2
90/10 42.7 294 41.1 283 3.7
80/20 40.0 276 37.1 256 7.2
73/27 38.1 263 34.3 236 10.0
HFC-161/HFC-3-10-lsy(-20℃)
99/1 31.1 214 31.0 214 0.3
90/10 29.7 205 28.6 197 3.7
80/20 28.1 194 25.9 179 7.8
75/25 27.2 188 24.6 170 9.6
74/26 27.1 187 24.3 168 10.3
HFC-161/ butane (20 ℃)
99/1 31.1 214 31.0 214 0.3
90/10 29.8 205 29.1 201 2.3
80/20 28.4 196 26.9 185 5.3
70/30 26.9 185 24.6 170 8.6
67/33 26.5 183 23.9 165 9.8
66/34 26.3 181 23.6 163 10.3
HFC-161/ Trimethylmethane (20 ℃)
99/1 31.2 215 31.2 215 0.0
90/10 30.5 210 30.3 209 0.7
80/20 29.6 204 29.0 200 2.0
70/30 28.6 197 27.5 190 3.8
60/40 27.4 189 25.6 177 6.6
52/48 26.4 182 23.9 165 9.5
51/49 26.3 181 23.6 163 10.3
HFC-161/DME(-30℃)
1/99 11.6 80.0 11.6 80.0 0.0
10/90 12.4 85.5 12.1 83.4 2.4
20/80 13.2 91.0 12.7 87.6 3.8
30/70 14.1 97.2 13.3 91.7 5.7
40/60 15.0 103 14.1 97.2 6.0
50/50 16.0 110 15.0 103 6.3
60/40 17.0 117 16.0 110 5.9
70/30 17.9 123 17.1 118 4.5
80/20 18.9 130 18.3 126 3.2
90/10 19.9 137 19.6 135 1.5
99/1 20.8 143 20.8 143 0.0
HFC-281ea/HFC-134a(-10℃)
1/99 29.1 201 29.0 200 0.3
10/90 26.7 184 25.6 177 4.1
20/80 24.4 168 22.7 157 7.0
30/70 22.4 154 20.4 141 8.9
40/60 20.6 142 18.8 130 8.7
50/50 19.1 132 17.5 121 8.4
60/40 17.8 123 16.5 114 7.3
70/30 16.7 115 15.8 109 5.4
80/20 15.7 108 15.1 104 3.8
90/10 14.9 103 14.6 101 2.0
99/1 14.2 97.9 14.2 97.9 0.0
HFC-281ea/HFC-152a(-20℃)
1/99 17.8 123 17.8 123 0.0
10/90 17.0 117 16.6 114 2.4
20/80 16.0 110 15.3 105 4.4
30/70 15.1 104 14.2 97.9 6.0
40/60 14.2 97.9 13.2 91.0 7.0
50/50 13.3 91.7 12.3 84.8 7.5
60/40 12.4 85.5 11.6 80.0 6.5
70/30 11.6 80.0 10.9 75.2 6.0
80/20 10.8 74.5 10.2 70.3 5.6
90/10 10.0 68.9 9.68 66.7 3.2
99/1 9.28 64.0 9.23 63.6 0.5
HFC-281ea/HFC-3-10-lsy(0℃)
99/1 21.0 145 20.9 144 0.5
90/10 20.3 140 20.1 139 1.0
80/20 19.6 135 19.1 132 2.6
70/30 18.8 130 18.0 124 4.3
60/40 17.9 123 16.9 117 5.6
50/50 17.0 117 15.7 108 7.6
41/59 16.1 111 14.5 100 9.9
40/60 16.0 110 14.3 98.6 10.6
HFC-281ea/ propane (10 ℃)
1/99 35.3 344 49.8 343 0.2
10/90 48.6 335 48.1 332 1.0
20/80 47.1 325 45.7 315 3.0
30/70 45.4 313 42.9 296 5.5
40/60 43.4 299 39.3 271 9.4
41/59 43.2 298 38.9 268 10.0
HFC-281ea/DME(-9.95℃)
1/99 26.7 184 26.7 184 0.0
10/90 25.8 178 25.4 175 1.6
20/80 24.8 171 24.1 166 2.8
30/70 23 7 163 22.7 157 4.2
40/60 22.5 155 21.3 147 5.3
50/50 21.3 147 20.0 138 6.1
60/40 20.0 138 18.7 129 6.5
70/30 18.7 129 17.5 121 6.4
80/20 17.3 119 16.3 112 5.8
90/10 15.9 110 15.2 105 4.4
99/1 14.4 99.3 14.3 98.6 0.7
HFC-3-10-lsy/HFC-134(-21.7℃)
13.9/86.1 14.7 101.4 14.7 101.4 0.0
7/93 14.5 100.0 14.3 98.6 1.4
1/99 13.7 94.5 13.5 93.1 1.5
0/100 13.4 92.4 13.4 92.4 0.0
20/80 14.6 100.7 14.6 100.7 0.0
30/70 14.5 100.0 14.2 97.9 2.1
40/60 14.3 98.6 13.5 93.1 5.6
44/56 14.2 97.9 12.8 88.3 9.9
45/55 14.2 97.9 12.6 86.9 11.3
100/0 3.89 26.8 3.89 26.8 0.0
HFC-3-10-lsy/HFC-134a(0℃)
1/99 42.9 296 42.9 296 0.0
5/95 42.3 292 42.1 290 0.5
10/90 41.5 286 40.8 281 1.7
15/85 40.6 280 39.4 272 3.0
20/80 39.7 274 38.0 262 4.3
25/75 38.9 268 36.4 251 6.4
30/70 38.0 262 34.7 239 8.7
32/68 37.7 260 34.0 234 9.8
33/67 37.5 259 33.6 232 10.4
HFC-3-10-lsy/HFC-152a(0℃)
1/99 38.4 265 38.4 265 0.0
10/90 36.8 254 36.0 248 2.2
20/80 35.0 241 33.1 228 5.4
30/70 33.2 229 30.0 207 9.6
31/69 33.0 228 29.6 204 10.3
HFC-3-10-lsy/HFC-236ea(-1.7℃)
33.6/66.4 14.7 101 14.7 101 0.0
20/80 14.5 100 14.1 97.0 2.9
11/89 13.8 94.9 12.4 85.5 9.9
50/50 14.6 100 14.3 98.5 1.9
60/40 14.4 99.3 13.2 90.7 8.7
61/39 14.4 99.3 12.9 88.9 10.4
100/0 8.91 61.4 8.91 61.4 0.0
0/100 10.4 71.7 10.4 71.7 0.0
1/99 11.0 75.6 10.5 72.3 4.4
3/97 11.9 81.8 10.7 73.9 9.7
HFC-3-10-lsy/HFC-236fa(-2.5℃)
12.7/87.3 14.7 101 14.7 101 0.0
1/99 14.2 98.0 14.2 97.8 0.2
0/100 14.1 97.2 14.1 97.2 0.0
40/60 13.9 95.6 13.2 91.1 4.7
50/50 13.4 92.1 12.2 84.0 8.8
52/48 13.2 91.3 12.0 82.5 9.7
53/47 13.2 90.9 11.8 81.6 10.2
100/0 8.64 59.6 8.64 59.6 0.0
HFC-3-10-lsy/ butane (0 ℃)
1/99 14.9 103 14.9 103 0.0
10/90 14.6 101 14.5 99.8 0.7
20/80 14.2 97.7 14.0 96.4 1.3
30/70 13.7 94.7 13.5 92.7 2.0
40/60 13.3 91.4 12.9 88.9 2.7
50/50 12.8 87.9 12.3 85.1 3.2
60/40 12.2 84.1 11.8 81.1 3.6
70/30 11.6 80.0 11.2 77.1 3.7
80/20 11.0 75.6 10.6 73.1 3.4
90/10 10.3 70.8 10.0 69.2 2.2
99/1 9.59 66.1 9.56 65.9 0.3
HFC-3-10-lsy/ Trimethylmethane (0 ℃)
1/99 22.6 156 22.6 156 0.0
10/90 21.7 150 21.3 147 2.1
20/80 20.7 143 19.8 136 4.3
30/70 19.6 135 18.3 126 6.5
40/60 18.4 127 16.8 116 8.8
45/55 17.8 123 16.0 111 9.9
46/54 17.7 122 15.9 110 10.1
88/12 11.6 80.2 10.5 72.1 10.1
89/11 11.5 79.0 10.4 71.5 9.5
99/1 9.69 66.8 9.57 66.0 1.2
HFC-3-10-lsy/ propane (20 ℃)
1/99 35.2 243 35.0 241 0.6
10/90 33.5 231 31.9 220 4.8
19/81 31.6 218 28.6 197 9.5
20/80 31.4 216 28.2 194 10.2
HFC-3-10-lsy/DME(-10℃)
1/99 26.7 184 26.7 184 0.0
10/90 26.0 179 25.7 177 1.2
20/80 25.1 173 24.4 168 2.8
30/70 24.2 167 22.9 158 5.4
40/60 23.2 160 21.1 145 9.1
42/58 23.0 159 20.7 143 10.0
43/57 22.8 157 20.5 141 10.1
The result of this example shows because after the former composition of 50% (weight) is removed, the variation of the vapour pressure of 25 ℃ of remaining set compounds greatly about former composition vapour pressure 10% in, so these compositions are azeotrope or Azeotrope-like.
Example 3
The influence of steam seepage in the time of-20 ℃
Carry out leak testing-20 ℃ the time with the composition of HFC-3-10-lsy and HFC-236fa.The result is summarized as follows." A " represents HFC-3-10-lsy, and " B " represents HFC-236fa.
After initiator 50% leaks
The weight % of the weight %/B of A PSIA KPA PSIA KPA DELTA%P
HFC-3-10-lsy/HFC-236fa
16.3/83.7 6.86 47.3 6.86 47.3 0.0
10/90 6.82 47.0 6.80 46.9 0.3
1/99 6.49 44.7 6.47 44.6 0.3
30/70 6.75 46.5 6.66 45.9 1.3
40/60 6.59 45.4 6.34 43.7 3.8
50/50 6.37 43.9 5.90 40.7 7.4
55/45 6.25 43.1 5.63 38.8 9.9
56/44 6.22 42.9 5.58 38.5 10.3
These results show that the composition of HFC-3-10-lsy and HFC-236fa is azeotrope or Azeotrope-like under differing temps, but the weight percent of these components changes along with variation of temperature.
Example 4
Vapour pressure and kauri-butanol number (Kauri-butanol value)
The vapour pressure of compound of the present invention provides below.Data show that these compounds can effectively substitute the hydro carbons that nowadays is widely used in the aerosol preparaton.HFC-281ea and Trimethylmethane and HFC-161 and propane have almost equal vapour pressure.The kauri-butanol number of compound of the present invention also is higher than each corresponding hydrocarbon.This show these compounds have better dissolving power and better and the aerosol resin and with the consistency of other activeconstituentss.
Vapour pressure (Psig) kauri-butanol number
70°F 130°F
HFC-161 106 264 16.3
HFC-281ea 31 99 20.3
HFC-3-10-lsy 5 38 -
Propane 108 262 15
Trimethylmethane 31 97 18
Butane 17 65 20
Example 5
VOC (volatile organic compounds) judges
Carrying out kinetic rate with experimental technique (in the jet propulsion laboratory) measures, perhaps judge compound of the present invention (reference: Kwok with the radical reaction method of R.Atkinson, E.S.C., with R.Atkinson work " with the hydroxyl radical free radical reaction velocity constant of structure-reactivity relation measuring and calculating gas phase organic compound; revised edition ", to the final report (FR) of CMA, contract number ARC-8.0-OR, 1994).If when 298k, be standard with ethane, a kind of kinetic rate of compound is less than 1.0, and this compound can be considered to right and wrong VOC.The results are shown in the following table.
Table
CompoundK, at 298K, cm 3/ molecule-second k measures or judges with respect to ethane
With respect to the OH free radical reaction
Ethane 2.4 * 10 -131.0 measure
Propane 1.1 * 10 -124.6 measure
Butane 2.54 * 10 -1210.5 judge
Trimethylmethane 2.33 * 10 -129.7 judge
HFC-161 1.7 * 10 -130.7 measure
HFC-281ea 4.6 * 10 -131.9 measure
HFC-3-10-lsy 7.7 * 10 -140.3 judge
Compound of the present invention with nowadays be widely used in aerocolloidal propane, these hydro carbons of butane and Trimethylmethane are compared, its photochemical (hydroxyl radical free radical) activity significantly reduces.In aerosol, use compound of the present invention can significantly reduce ground smog.Because the activity of HFC-161 and HFC-3-10-lsy is lower than ethane,, they are non-VOC so being incorporated into.The activity of HFC-281ea is starkly lower than its hydro carbons resemblance Trimethylmethane.
Example 6
55%VOC ulv spraying experiment example
55%VOC of the present invention (volatile organic compounds) ulv spraying preparaton is formulated as follows:
Table
% (weight)
Octyl acrylamide/acrylate/butyl amino-ethyl methyl
Acrylate copolymer (National Starch) 5.00
AMP (2-amino-2-methyl-1-propanol, Kodak) 0.96
Dimethicone Silylate(Hydrolabs) 0.50
Water 3.54
In this mixture, add ethanol and propelling agent of the present invention, form the 55%VOC preparaton:
Weight %/weight % Alcoholic acid weight %
HFC-161 35.00 55.00
HFC-3-10-lsy 35.00 55.00
HFC-161/HFC-134a 5.00/30.00 55.00
HFC-161/HFC-152a 5.00/30.00 55.00
HFC-161/HFC-281ea 35.00/7.00 48.00
HFC-161/HFC-3-10-lsy 28.00/7.00 55.00
HFC-281ea/HFC-134a 7.00/35.00 48.00
HFC-281ea/HFC-152a 7.00/35.00 48.00
HFC-281ea/HFC-3-10-lsy 7.00/35.00 48.00
HFC-3-10-lsy/HFC-134 5.00/30.00 55.00
HFC-3-10-lsy/HFC-134a 5.00/30.00 55.00
HFC-3-10-lsy/HFC-152a 7.00/28.00 55.00
The vapor pressure of each mixture may change with preparaton.This example is descriptive, is not the optimization system.
Example 7
55%VOC ulv spraying experiment example
Two kinds are formulated as follows according to 55%VOC ulv spraying preparaton of the present invention:
Component A B
Wt％ Wt％
PVM/MA multipolymer 6.00 6.00
AMP 0.35 0.35
Water 29.05 38.65
Ethanol 40-1 34.60 25.00
By weight, in these mixtures, add one of following composition of the present invention of 30%, to form the preparaton of 55%VOC:
Table
Prescription
Component A B
Wt％ Wt％
HFC-161/DME 9.60/20.40 -
HFC-161/ butane 9.60/20.40-
HFC-161/ Trimethylmethane 9.60/20.40-
HFC-161/DME - 9.60/20.40
HFC-281ea/ propane-9.60/20.40
HFC-281ea/DME 9.60/20.40 -
HFC-3-10-lsy/ butane 9.60/20.40-
HFC-3-10-lsy/ propane 9.60/20.40-
HFC-3-10-lsy/DME 9.60/20.40 -
HFC-3-10-lsy/ Trimethylmethane 9.60/20.40-
The vapor pressure of every kind of mixture may change with preparaton.This example is descriptive, does not reflect the optimization system.Because HFC-281ea has significantly low photochemical activity, will be littler to the influence of smog on the ground than those preparatons that contain hydro carbons so contain the preparaton of HFC-281ea.
Example 8
The aromatising flavour experimental example
As follows according to aromatising flavour experiment preparaton of the present invention:
Wt％
Fragrance thing 3.0
Ethanol 40-1 70.0
Water 15.0
By weight, one of following mixture of the present invention of adding 12.0% in this mixture:
Wt％ ％VOC
HFC-161 12.0 70
HFC-281ea 12.0 82
HFC-3-10-lsy 12.0 70
HFC-161/HFC-134a 3.0/9.0 70
HFC-161/HFC-152a 3.0/9.0 70
HFC-161/HFC-281ea 9.0/3.0 73
HFC-161/HFC-3-10-lsy 9.0/3.0 70
HFC-161/ butane 9.0/3.0 73
HFC-161/ Trimethylmethane 9.0/3.0 73
HFC-161/DME 6.0/6.0 76
HFC-281ea/HFC-134a 3.0/9.0 73
HFC-281ea/HFC-152a 3.0/9.0 73
HFC-281ea/HFC-3-10-lsy 3.0/9.0 73
HFC-281ea/ propane 3.0/9.0 82
HFC-281ea/DME 3.0/9.0 82
HFC-3-10-lsy/HFC-134 2.0/10.0 70
HFC-3-10-lsy/HFC-134a 3.0/9.0 70
HFC-3-10-lsy/HFC-152a 3.0/9.0 70
HFC-3-10-lsy/ butane 5.0/4.0 74
HFC-3-10-lsy/ Trimethylmethane 4.0/5.0 75
HFC-3-10-lsy/ propane 2.0/10.0 80
HFC-3-10-lsy/DME 3.0/9.0 79
The vapor pressure of every kind of mixture may change with preparaton.This example is descriptive, does not reflect the optimization system.Because HFC-281ea has significantly low photochemical activity, will be littler to the influence of ground smog than those preparatons that contain hydro carbons so contain the preparaton of HFC-281ea.
Example 9
The anti-sweat of aerosol oozes experimental example
It is as follows to ooze the experiment preparaton according to the anti-sweat of 66%VOC aerosol of the present invention:
Table
Wt％
Wickenol CPS 325 10.0
Isopropyl myristate 6.0
Polysiloxane fluid (Dow Corning) DC-344 6.0
Talcum powder 0.5
Quaternium-18 hectorite 0.5
Ethanol 40-1 2.0
To join in this mixture with one of the following mixture of the present invention of every kind 75.0% (weight), to form the preparaton of 60%VOC.
HFC-161/DME 17.0/58.0
The HFC-161/ butane 17.0/58.0
The HFC-161/ Trimethylmethane 17.0/58.0
The HFC-3-10-lsy/ butane 17.0/58.0
The HFC-3-10-lsy/ Trimethylmethane 17.0/58.0
HFC-3-10-lsy/ propane 17.0/58.0
HFC-3-10-lsy/DME 17.0/58.0
Use the present composition also can develop air freshener, home disinfecting agent, insecticidal aerosol and similarly preparaton such as spray paint.
Example 10
Hair sprays performance
Below example by with widely used hydrogen fluorocarbon propellant HFC-152a (CH 3CHF 2) compare, shown the effect of the present invention aspect the hair sprays, listed as following table.These preparatons all are single phases, show that they are mixable fully.With viscosity and time of drying, curl sagging and its performance is estimated in length of flame test (flame extention test).The elongation of sagging measurement frizz after spraying 5 minutes curls.Measuring the length of flame is the combustibility of measuring each preparaton.The result shows that each preparaton all reaches 80% or higher curling reservation amount, good viscosity and time of drying; Although preparaton is without optimization, its length of flame result is still acceptable.
Table
Preparaton
Component (Wt%) A B C D E F G H
Resin * 25 25 25 25 25 19.5 19.5 19.5
Ethanol 43 43 43 43 43 35.0 35.0 35.0
Additive 22222 1.7 1.7 1.7
HFC-161 - 30 - 18 - - - 10.0
HFC-281ea - - 30 - 12 - 10.0 -
HFC-152a 30 - - - 18 10.0 - -
Butane---12----
Water-----13.8 13.8 13.8
DME - - - - - 20.0 20.0 20.0
Gross weight % 100 100 100 100 100 100 100 100
Vapour pressure 60 95 31 79 52 47 40 64
@70°F(psig)
％VOC 43 43 73 55 55 55 65 55
Sagging % 9 21 11 17 16 18 11 17 curls
(sec) 10 14 47 11 8 14 58 is clamminess the time
Time of drying (sec) 24 28 17 46 54 21 39 73
The length of flame 4694 13 4 12 16
(inch)
* tert-butyl acrylate/ethyl propenoate/Sipacril 2739OF resin
Example 11
The air freshener performance
But combustibility and compatibility in order to test air freshener are mixed with air freshener according to prescription listed in the following table with composition of the present invention.These preparatons all are single phases, show that they are mixable fully.Measure length of flame value less than 18 inches maximum permissible values.These preparatons have good spray pattern and discharge performance.
Table
Preparaton
Component A Wt％ B Wt％
Spices 1 1
Water 4 4
Ethanol 30 30
HFC-161 65 -
HFC-281ea - 65
Gross weight % 100 100
Zheng Qiya @70F (psig) 106 33
The length of flame (inch) 13 16
Example 12
The fragrance performance
But combustibility and compatibility in order to test perfume compound are mixed with perfume compound according to preparaton listed in the following table with composition of the present invention.These preparatons all are single phases, show that they are mixable fully.Measure length of flame value less than 18 inches maximum permissible values.These preparatons have good spray pattern and efficient.
Table
Preparaton
Component A Wt％ B Wt％
Spices 3 3
Ethanol 70 70
Water 15 15
HFC-161 12 -
HFC-281ea - 12
100 100
Zheng Qiya @70F (psig) 46 14
The length of flame (inch) 13 10
Example 13
Package stability
The composition that the preparation following table is listed also installs in the aerosol canister of tin-coated steel leather.These jars are placed in 120 the stove or keep some months under room temperatures (21-23 ℃).
Table
Composition temperature-time jar inside
120 2 months non-corrodings of HFC-161/ ethanol
(30/70% (weight)) slight detin
6 months non-corrodings
The moderate detin
24 months non-corrodings of FC-161/ ethanol room temperature
(30/70% (weight)) slight detin
120 1 month non-corrodings of HFC-281ea/ ethanol or detin
(60-40% (weight)) 3 months non-corrodings or detin
1 month non-corroding in HFC-281/ ethanol/120 or detin
Water (40/54/6% (weight))
As showing in the table that in the preparaton solvent, even do not have under the situation of rust-preventive agent, this composite spray shows satisfactory stability.
Example 14
Following table is listed the performance of various cooling agent.These data are based on that following condition obtains.
45.0 of evaporator temperatures (7.2 ℃)
130.0 of condenser temperatures (54.4 ℃)
15.0 of condensate depression (8.3 ℃)
Return 65.0 of gases (18.3 ℃)
Compressor efficiency is 75%
Refrigerating capacity is that 3.5 cubic chis of per minutes, volumetric efficiency are the refrigerating capacity of 75% compressor according to fixing displacement.Freezing capacity is meant the variation at every pound of cooling agent enthalpy of vaporizer internal recycle, the i.e. heat of at every turn being taken away by the cooling agent in the vaporizer.Operating factor (COP) is meant the ratio of the merit that freezing capacity and compressor are done, and it is to weigh cooling agent refrigeration effect.
Freezing capacity
Refrigerant evaporator pressure condenser pressure compressor operating capacity BTU/ minute
Composition Psia (kPa) Psia (kPa) Temperature (℃) COP (kW)
HFC-161/HFC-134a
1/99 55 379 215 1482 171 77 3.43 225 4.0
99/1 80 552 279 1924 201 94 3.49 316 5.6
HFC-161/HFC-152a
1/99 51 352 194 1338 204 96 3.60 224 3.9
99/1 90 552 278 1917 200 93 3.53 318 5.6
HFC-161/HFC-281ea
1/99 27 186 106 731 168 76 3.71 123 2.2
99/1 79 545 278 1917 201 94 3.49 314 5.5
HFC-161/HFC-3-10-lsy
1/99 13 90 55 379 148 64 3.75 63 11
99/1 79 545 277 1910 201 94 3.50 314 5.5
The HFC-161/ butane
1/99 20 138 82 565 155 68 3.68 93 1.6
99/1 79 545 277 1910 201 94 3.49 314 5.5
The HFC-161/ Trimethylmethane
1/99 30 207 65 448 112 44 3.57 123 2.2
99/1 79 545 279 1924 201 94 3.49 315 5.5
HFC-161/DME
1/99 49 338 183 1262 194 90 3.67 215 3.8
99/1 79 545 279 1924 201 94 3.49 315 5.5
HFC-218ea/HFC-134a
1/99 54 372 212 1462 171 77 3.43 222 3.9
99/1 27 186 105 724 168 76 3.70 121 2.1
HFC-281ea/HFC-152a
1/99 50 345 192 1324 204 95 3.61 222 3.9
99/1 27 186 105 724 168 76 3.70 122 2.1
HFC-281ea/HFC-3-10-lsy
1/99 12 83 54 372 148 64 3.68 59 1.0
99/1 26 179 104 717 168 76 3.70 120 2.1
HFC-281ea/ propane
1/99 83 572 270 1862 166 74 3.32 282 5.0
99/1 27 186 107 738 168 76 3.71 123 2.2
HFC-281ea/DME
1/99 48 331 181 1248 193 89 3.68 213 3.8
99/1 27 186 106 731 168 76 3.70 122 2.1
HFC-3-10-sy/HFC-134a
1/99 42 290 167 1151 182 83 3.60 187 3.3
99/1 12 83 54 372 148 64 3.69 60 1.1
HFC-3-10-lsy/HFC-134a
1/99 54 372 210 1448 171 77 3.44 221 3.9
99/1 12 83 54 372 148 64 3.69 60 1.1
HFC-3-10-lsy/HFC-152a
1/99 50 345 191 1317 203 95 3.60 221 3.9
99/1 13 90 54 372 148 64 3.70 60 1.1
HFC3-10-lsy/HFC-236ea
1/99 15 103 70 483 143 62 3.50 71 1.3
99/1 12 83 53 365 148 64 3.67 59 1.0
HFC-3-10-lsy/HFC-236fa
1/99 20 138 86 593 141 60 3.42 86 1.5
99/1 12 83 53 365 148 64 3.67 59 1.0
The HFC-3-10-lsy/ butane
1/99 19 131 80 552 155 68 3.65 90 1.6
99/1 12 83 53 365 148 64 3.67 59 1.0
The HFC-3-10-lsy/ Trimethylmethane
1/99 29 200 110 758 152 67 3.56 120 2.1
99/1 12 83 54 372 148 64 3.68 59 1.0
HFC-3-10-sy/ propane
1/99 83 572 269 1855 166 74 3.33 281 4.9
99/1 13 90 55 379 147 64 3.74 62 1.1
HFC-3-10-lsy/DME
1/99 48 331 181 1248 193 89 3.67 213 3.7
99/1 13 90 55 379 148 64 3.73 62 1.1
Additional compound
Can in above-mentioned these azeotropes or Azeotrope-like, add other components, and not change the character of composition basically, comprise the azeotropic behavior that does not change it and show.These other components that are added have, for example boiling point is-60 to+60 ℃ a fat hydrocarbon, boiling point is-60 to+60 ℃ a hydrogen fluorine carbon alkane class, boiling point is the hydrofluoropropane class between-60 to+60 ℃, boiling point is the hydrocarbon ester class between-60 to+60 ℃, and boiling point is the hydrochlorofluorocarazeotropic class between-60 to+60 ℃, and boiling point is-60 to+60 ℃ a hydrogen fluorine carbon, hydrogen chlorine carbon class, chloro-hydrocarbons and the perfluorochemical of boiling point between-60 to+60 ℃.
Additive such as lubricant, rust-preventive agent, tensio-active agent, stablizer, dyestuff and other suitable materials can join in the novel compositions of the present invention to reach various purposes, as long as they can not produce adverse influence to composition in its intended purpose.Preferred lubricant comprises that molecular weight is greater than 250 ester class.

Claims (4)

1. azeotropic or Azeotrope-like compositions, said composition is made up of following material basically: the 2-fluoropropane of the fluoroethane of 73-99 weight % and 1-27 weight %; The tertiary butyl fluorochemical of the fluoroethane of 75-99 weight % and 1-25 weight %; The butane of the fluoroethane of 67-99 weight % and 1-33 weight %; The Trimethylmethane of the fluoroethane of 52-99 weight % and 1-48 weight %; The dimethyl ether of the fluoroethane of 1-99 weight % and 1-99 weight %; 1,1,1 of the 2-fluoropropane of 1-99 weight % and 1-99% weight, the 2-Tetrafluoroethane; 1 of the 2-fluoropropane of 1-99 weight % and 1-99 weight %, the 1-C2H4F2 C2H4F2; The 2-fluoropropane of 41-99 weight % and the tertiary butyl fluorochemical of 1-59%; The propane of the 2-fluoropropane of 1-41 weight % and 59-99 weight %; The dimethyl ether of the 2-fluoropropane of 1-99 weight % and 1-99 weight %; 1,1,2 of the tertiary butyl fluorochemical of 1-44 weight % and 56-99 weight %, the 2-Tetrafluoroethane; 1,1,1 of the tertiary butyl fluorochemical of 1-32 weight % and 68-99 weight %, the 2-Tetrafluoroethane; 1 of the tertiary butyl fluorochemical of 1-30 weight % and 70-99 weight %, the 1-C2H4F2 C2H4F2; 1,1,1,2,3 of the tertiary butyl fluorochemical of 11-60 weight % and 40-89 weight %, the 3-HFC-236fa; 1,1,1,2,3 of the tertiary butyl fluorochemical of 1-3 weight % and 97-99 weight %, the 3-HFC-236fa; 1,1,1,3,3 of the tertiary butyl fluorochemical of 1-52 weight % and 48-99 weight %, the 3-HFC-236fa; The butane of the tertiary butyl fluorochemical of 1-99 weight % and 1-99 weight %; The Trimethylmethane of the tertiary butyl fluorochemical of 1-45 weight % and 55-99 weight %; The Trimethylmethane of the tertiary butyl fluorochemical of 89-99 weight % and 1-11 weight %; The propane of the tertiary butyl fluorochemical of 1-19 weight % and 81-99 weight %; Or the dme of the tertiary butyl fluorochemical of 1-42 weight % and 58-99 weight %.
2. make aerocolloidal method for one kind, comprise the composition that uses claim 1.
3. the method for a refrigeration comprises the composition of condensation claim 1 making the evaporation around needs refrigerative object of described composition then.
4. a method of making thermoset or thermoplastic foam comprises that the composition that uses claim 1 is as whipping agent.
CNB971995761A 1996-11-04 1997-11-03 Hydrofluorocarbon compositions Expired - Fee Related CN1181155C (en)

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